A kind of process for forming magnesium alloy ultra-fine thin-wall tube that is used for degradable blood vessel bracket
Technical field:
The present invention relates to a kind of ultra-fine thin-wall tube forming technology that is used for intravascular stent, particularly a kind of process for forming magnesium alloy ultra-fine thin-wall tube that is used for degradable blood vessel bracket.
Technical background:
Adopting the intravascular stent interventional therapy is one of main method of treatment cardiovascular disease.The intravascular stent of clinical practice at present is main preparation material with rustless steel and NiTi alloy.These intravascular stents exist in the process of treatment:
1) Ni ion stripping may cause toxic and side effects;
2) vascellum endometrial hyperplasia has generation vascular restenosis and thrombosis more than 20% approximately;
3) chronic inflammatory disease, Antiplatelet therapy time are long, need long-term medication treatment;
4) (blood vessel of implant frame) can't adapt to the self-sow of blood vessel, is unfavorable for young patient especially;
Can't carry out surgery vascular reconstruction (second operation) when 5) accident occurring;
6) secular endothelium disorder;
7) follow-up monitoring difficulty can't be used MRI.
With respect to rustless steel and NiTi alloy material, magnesium alloy has low-down standard electrode potential, is being rich in Cl
-Can reach vivo degradation by the mode of metal erosion in ionic human body fluid and the blood.Existing experiment in vitro and animal Implantation Test have all been verified this conclusion, and magnesium alloy can be degraded in human body and be built consensus in bio-medical material research circle.And the magnesium ion indispensable trace element that is human body, it participates in multiple metabolism, and excessive magnesium ion can excrete with urine, so the magnesium ion that forms after the magnesium alloy degradation in vivo can not work the mischief to human body.
Summary of the invention:
The objective of the invention is at the ubiquitous non-degradable problem of present medical metal vascular stent material, utilizing the perishable degradation characteristic and the magnesium of magnesium is the characteristics of indispensable trace element in the human body, a kind of forming technology of magnesium alloy ultra-fine thin-wall tube of degradable blood vessel bracket is provided, can realize the vivo degradation of medical metal embedded material, replace original non-degradable support, can improve the clinical serviceability of implant devices and improve patient's health status.
The object of the present invention is achieved like this: the design that at first is material, it is characterized in that, in pure magnesium, add yttrium (Y), mishmetal (RE), aluminum (Al), calcium (Ca), manganese (Mn), antimony (Sb), zinc (Zn), eight kinds of alloying elements of zirconium (Zr) make this kind magnesium alloy materials have high strength, good plasticity, high corrosion-resistant and excellent biological compatibility, thereby guarantee this kind magnesium alloy needed enough mechanical properties and better machining property in application, and magnesium has less spot corrosion tendency under the human body environment and to the harmless effect of human body.The mass percent of each alloying element in this kind magnesium alloy materials is: Y 1~5%, and RE 0.1~1%, Al0.01~0.9%, Ca 0.01~1%, and Zn 0.1~1%, and Mn 0.1~1.5%, Sb 0.1~1%, and Zr 0.1~1%, and Mg 87.6~98.48%.
Will carry out melting to magnesium alloy add alloying element in pure magnesium after, its technical process is:
In the melting preparation of magnesium alloy, employing gas shield melting+fall the method for ferrum solvent refined reduces the impurity content in the alloy significantly, and the degree of purity level of magnesium alloy is reached more than 99.95%.
Adopt the process forming of hot extrusion deformation to go out extruded bar from magnesium alloy, eliminate pore in the alloy, casting flaw such as loose, the crystallite dimension of refinement magnesium alloy, thus improve its intensity and plasticity.
By to the magnesium alloy heat treatment, further eliminate the component segregation in the alloy, improve alloy in composition and structural uniformity, make intensity, plasticity and the corrosion resistance of alloy obtain best fit.
The magnesium alloy materials that obtains at last tensile strength at room temperature is not less than 320MPa, and yield strength is not less than 260MPa, and percentage elongation is not less than 20%.
After magnesium alloy materials prepares, make ultra-fine thin-wall tube with magnesium alloy materials.Process for forming magnesium alloy ultra-fine thin-wall tube is as follows:
1, the magnesium alloy ingot that melts out is heated to 400 ℃~530 ℃, extrusion molding obtains extruded bar from magnesium alloy, and the intercepting certain-length is as the workpiece of following process.
2, the extruded bar from magnesium alloy with intercepting carries out solution treatment, quenches in the back of coming out of the stove.
3, workpiece one end with intercepting is processed into tubulose, and the other end is processed into bar-shaped, and the external diameter of workpiece pipe end is greater than the diameter of workpiece rod end.Use conical surface transition between workpiece rod end and the workpiece pipe end.Wall thickness after the workpiece pipe end machining is between 0.2mm~1mm.
4, the drawing sample after the machining being carried out solution treatment, quenches in the back of coming out of the stove.
5, with the drawing plastic forming process processed workpiece pipe end is carried out tube reducing, empty mode of drawing is adopted in drawing, the workpiece pipe end to be heated to 400 ℃~500 ℃ before the drawing, drawing branch passage is carried out, every time sizing reduction is 0.1mm~1mm, through the multi-pass drawing, the diameter that finally can be shaped is at 2~10mm, wall thickness evenly, at the ultra-fine thin-wall tube of 0.20mm~1mm.
6, the ultra-fine thin-wall tube after the drawing being carried out solution treatment, quenches in the back of coming out of the stove.
7, surface finish.
Advantage of the present invention is the limitation that has overcome forming technologies such as extruding, adopts gas shield melting, hot extrusion deformation, machining, drawing and heat treatment series of process to be shaped and to be used for the magnesium alloy ultra-fine thin-wall tube of degradable blood vessel bracket.This technology cost is lower, and the tube wall thickness of shaping is even, even tissue and mechanical property better performances.
Description of drawings:
Fig. 1 is drawing workpiece and drawing mould user mode figure
The specific embodiment:
Below in conjunction with embodiment the present invention is described in further details:
Embodiment 1
As shown in Figure 1, (1) is the workpiece pipe end, and (2) are drawing mould, and (3) are the workpiece transition conical surface, and (4) are workpiece rod end, and (5) are the mould conical surface, and (6) are the mould metering hole.The diameter of the pipe end of drawing workpiece (1) is bigger than mould metering hole (6), and the diameter of workpiece rod end (4) is slightly less than mould metering hole (6).The workpiece transition conical surface (3) matches with the mould conical surface (5).At first workpiece rod end (4) is passed mould metering hole (6), then whole work-piece and drawing mould (2) are placed on the drawbench, workpiece rod end (4) carries out drawing with the chuck chucking of drawbench.Before drawing, workpiece pipe end (1) be heated, heating-up temperature is 400~500 ℃, insulation 10~20min to reduce its resistance of deformation, is convenient to drawing.According to the requirement of finished size, the design drawing passes.Through after the drawing of several passages, can obtain the ultra-fine thin-wall tube of required size.Ultra-fine thin-wall tube after the drawing need carry out solution treatment, quenches in the back of coming out of the stove, and makes it have better percentage elongation on certain intensity based possessing.
Embodiment 2: obtain diameter is that 2.5mm, wall thickness are the magnesium alloy ultra-fine thin-wall tube of 0.3mm, and each alloying element mass percent of this kind magnesium alloy is: Y 2%, and RE 0.5%, and Al 0.1%, Ca 0.02%, Zn0.4%, and Mn 0.6%, Sb 0.6%, and Zr 0.5%, and Mg 95.28%.The ingot casting that at first needs to melt out obtains the extruded bars that diameter is 7mm, and intercepts the solution treatment of 50~70mm progress row through hot extrusion deformation, and solid solubility temperature is between 450~500 ℃, and solution time is 8~16 hours, quenches in the back of coming out of the stove.Then workpiece pipe end (1) being machined into diameter is 5.5mm, and wall thickness is 0.3mm, and length is the drawing workpiece of 30mm, carries out Secondary Solid Solution Treatment, and solid solubility temperature is between 450~500 ℃, and solution time is 8~16 hours, quenches in the back of coming out of the stove.The mould metering hole (6) of drawing needs 5mm, 4.5mm, 4mm, 3.5mm, 3mm and six kinds of sizes of 2.5mm, just divides six passes of drawing.The size that the diameter of workpiece rod end (4) is slightly less than the drawing mould metering hole (6) of current pass gets final product.Before drawing, the pipe end (1) of workpiece be heated, temperature is 400~500 ℃, insulation 10~20min.After six passes of drawing, can obtain the uniform ultra-fine thin-wall tube of wall thickness.At last, under 450~500 ℃, solution treatment was quenched after 8~16 hours with the ultra-fine thin-wall tube after the drawing, carried out surface finish after the taking-up and handled.
Embodiment 3: obtain diameter is that 4mm, wall thickness are the magnesium alloy ultra-fine thin-wall tube of 0.5mm, and each alloying element mass percent of this kind magnesium alloy is: Y 4%, and RE 0.8%, and Al 0.5%, Ca 0.04%, and Zn 0.9%, and Mn 0.8%, Sb 0.3%, and Zr 0.4%, and Mg 92.26%.The ingot casting that at first needs to melt out obtains the extruded bars of 7mm through hot extrusion deformation, and intercepting 50~70mm is long, is carrying out solution treatment shrend after 4~8 hours under 470~520 ℃.Carefully the diameter of the pipe end (1) of rod is processed into 6.0mm then, and wall thickness is 0.5mm, and length is the drawing workpiece of 30mm, is carrying out Secondary Solid Solution Treatment shrend after 4~8 hours under 470~520 ℃ then.The metering hole of drawing mould (6) needs 5.5mm, 5mm, 4.5mm and four kinds of sizes of 4mm.Just divide the four-pass drawing.The size that the diameter of workpiece rod end (4) is slightly less than the drawing mould metering hole (6) of current pass gets final product.When drawing, the pipe end (1) of workpiece is heated to 400~500 ℃, insulation 10~20min.Through after the four-pass drawing, can obtain needed ultra-fine thin-wall tube like this.Ultra-fine thin-wall tube after the drawing in 500~520 ℃ of following solution treatment hot water quenching with 333~343K after 8~16 hours, is carried out the surface finish polishing after the taking-up.
Embodiment 4: obtain diameter is that 6mm, wall thickness are the magnesium alloy fine-radial light-wall pipe of 0.7mm, and each alloying element mass percent of this kind magnesium alloy is: Y 3%, and RE 1%, and Al 0.7%, Ca 0.06%, and Zn 0.4%, and Mn 0.5%, Sb 0.8%, and Zr 0.6%, and Mg 92.94%.The ingot casting that at first needs to melt out obtains the thin rod of diameter 10mm through hot extrusion deformation, and intercepting 50mm is long to carry out solution treatment shrend after 4~6 hours under 480~530 ℃.Carefully the diameter of the pipe end (1) of rod is processed into 8mm then, and wall thickness is 0.7mm, and length is 30mm, carries out Secondary Solid Solution Treatment then under 480~530 ℃, is incubated shrend after 4~6 hours.The metering hole of drawing mould (6) needs 7.5mm, 7mm, 6.5mm and four kinds of sizes of 6mm.Just divide the four-pass drawing.The size that the diameter of workpiece rod end (4) is slightly less than the drawing mould metering hole (6) of current pass gets final product.When drawing, the pipe end (1) of workpiece is heated to 400~500 ℃, insulation 10~20min.Through after the four-pass drawing, can obtain needed ultra-fine thin-wall tube like this.Ultra-fine thin-wall tube after the drawing is quenched after 4~6 hours 480~530 ℃ of following solution treatment, carry out the surface finish polishing after the taking-up.